Summary

For full-year courses in organic chemistry taken by science and pre-health professions majors.

This innovative text from acclaimed educator Paula Bruice is organized in a way that discourages rote memorization. It highlights mechanistic similarities and ties synthesis and reactivity together--teaching the reactivity of a functional group and the synthesis of compounds obtained as a result of that reactivity. Bruice's writing has been praised for anticipating students' questions and appeals to their need to learn visually and by solving problems. Emphasizing that students should reason their way to solutions rather than memorize facts, Bruice encourages students to think about what they have learned previously and apply that knowledge in a new setting. The text balances coverage of traditional topics with bioorganic chemistry, recognizing the importance of bioorganic topics to today's students.

Features

ISSUE: Students need pedagogy created by an experienced instructor who understands where they need help. PROBE: Will your students benefit from a text written by an instructor familiar with their struggles?

NEW--Revised many of the boxed materials--Bring topics to life and demonstrate the real-world relevance of the chemistry students are learning.

Piques student interest, increases confidence, and provides extra help for those who need it.

PROBLEM-SOLVING ISSUE: Students need to practice, practice, practice by solving problems. PROBE: Would your students benefit from a text particularly rich in problems and problem-solving pedagogy?

NEW--More in-chapter problems, more end-of-chapter problems, and more solved problems than almost any other textbook.

Helps students master the subject through problem solving.

NEW--Review of functional groups at beginning of Chapter 12. More spectroscopy problems added to chapters following treatment of spectroscopy (Chapters 12 and 13).

Allows instructors to introduce spectroscopy early in the course; improves instructors' ability to integrate spectroscopy throughout the second half of the course.

Problem-solving strategies--Offers at least one per chapter, followed by an exercise that enables students to immediately practice the strategy just discussed.

Teaches students how to approach certain kinds of problems, organize their thoughts, and improve their problem-solving abilities.

Solved problems--Walk students carefully through the different steps involved in solving a particular type of problem.

Gives students a framework to apply this process to other problems of the same type.

MEDIA ISSUE: Students' understanding can be greatly enhanced by a media package that is tightly correlated to the text. PROBE: Would integrated media resources, which expand the book's effectiveness improve your students' understanding of organic chemistry?

Author Bio

Table of Contents

(NOTE: Each chapter concludes with Key Terms and Problems. Chapters 3, 7-11, 14-20, and 27 conclude with a Summary of Reactions.)

I. AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY.

1. Electronic Structures and Bonding. Acids and Bases.

The Structure of an Atom. Distribution of Electrons in an Atom. Ionic, Covalent, and Polar Bonds. Lewis Structures. Atomic Orbitals. Molecular Orbitals and Bonding. Bonding in Methane and Ethane. Single Bonds. Bonding in Ethane. Double Bonds. Bonding in the Ethyne. Bonding in the Methyl Cation, the Methyl Radical, and the Methyl Anion. Bonding in Water. Bonding in Ammonia and in the Ammonium Ion. Bonding in the Hydrogen Halides. Summary of Orbital Hybridization, Bond Lengths, Bond Strengths, and Bond Angles. Dipole Moments of Molecules. An Introduction to Acids and Bases. Organic Acids and Bases: pKa and pH. The Effect of Structure on pKa. An Introduction to Delocalized Electrons and Resonance. The Effect of pH on the Structure of an Organic Compound. Lewis Acids and Bases.

2. An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure.

General Molecular Formula for a Hydrocarbon. Nomenclature of Alkenes. The Structure of Alkenes. Cis-Trans Isomerism. The E,Z System of Nomenclature. Reactivity Considerations. Thermodynamics and Kinetics. General Mechanism for Electrophilic Addition Reactions. Addition of Hydrogen Halides. Carbocation Stability. The Structure of the Transition State. Regioselectivity of Electrophilic Addition Reactions: Markovnikov's Rule. Addition of Water and Alcohols. Rearrangement of Carbocations. Addition of Halogens. Oxymercuration-Demercuration. Addition of Borane: Hydroboration-Oxidation. Addition of Radicals. The Relative Stabilities of Radicals. Addition of Hydrogen. The Relative Stabilities of Alkenes. Reactions and Synthesis.

4. Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions.

Conformational Isomers. Configurational Isomers: Cis-Trans Isomers. Configurational Isomers: Isomers with One Chirality Center. Drawing Enantiomers. Naming Enantiomers: The R, S System of Nomenclature. Optical Rotation. Optical Purity. Isomers with More Than One Chirality Center. Meso Compounds. The R, S System of Nomenclature for Isomers with More Than One Chirality Center. Reactions of Compounds That Contain a Chirality Center. Determining the Configuration. Separation of Enantiomers. Enantiotopic Hydrogens. Diastereotopic Hydrogens. and Prochirality Centers. Nitrogen and Phosphorus Chirality Centers. Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions. Stereochemistry of Alkene Addition Reactions. Stereochemistry of Enzyme-Catalyzed Reactions.

5. Reactions of Alkynes. Introduction to Multistep Synthesis.

Nomenclature of Alkynes. Physical Properties of Unsaturated Hydrocarbons. The Structure of Alkynes. Reactivity Considerations. Addition of Hydrogen Halides and Addition of Halogens. Addition of Water. Addition of Borane: Hydroboration-Oxidation. Addition of Hydrogen. Acidity of a Hydrogen Bonded to an sp Hybridized Carbon. Synthesis Using Acetylide Ions. Designing a Synthesis I: An Introduction to Multistep Synthesis. Commercial Use of Ethyne.

6. Electron Delocalization and Resonance.

Delocalized Electrons: The Structure of Benzene. Bonding in Benzene. Delocalized Electrons and Resonance. How to Draw Resonance Contributors. The Resonance Hybrid. Resonance Energy. Stability of Allylic and Benzylic Cations. Stability of Allylic and Benzylic Radicals. Some Chemical Consequences of Electron Delocalization. Effect of Delocalized Electrons on pKa. A Molecular Orbital Description of Stability.

7. Reactions of Dienes.

Nomenclature of Alkenes with More Than One Functional Group. Configurational Isomers of Dienes. Relative Stabilities of Dienes. A Molecular Orbital Description of 1,3-Butadiene. Reactivity Considerations. Electrophilic Addition Reactions of Isolated Dienes. Electrophilic Addition Reactions of Conjugated Dienes. Thermodynamic versus Kinetic Control of Reactions. Addition of a Dienophile to a Conjugated Diene: The Diels-Alder Reaction. Nomenclature of Bicyclic Compounds.

Reactivity Considerations. The Mechanism of SN2 Reactions. The SN2 Reaction. The Reversibility of an SN2 Reaction. The Mechanism of SN1 Reactions. The SN1 Reaction. The Stereochemistry of SN2 and SN1 Reactions. Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides. Competition between SN2 and SN1 Reactions. The Role of the Solvent in SN2 and SN1 Reactions. Biological Methylating Agents.

Nomenclature of Subsitituted Benzenes. Reactions of Substituents on Benzene. The Effect of Substituents on Reactivity. The Effect of Substituents on Orientaiton. The Effect of Substituents on pKa. The Ortho/Para Ratio. Additional Consideration Regarding Substituent Effects. Designing a Synthesis III: Synthesis of Monosubstituted and Disubstitued Benzenes. Synthesis of Trisubstitued Benzenes. Synthesis of Substitued Benzenes Using Arenadiazonium Salts. The Arenadiazonium Ion as an Electrophile. Mechanism for the Reaction of Amines with Nitrous Acid. Nucleophilic Aromatic Substitution Reactions. Benzyne. Polycyclic Benzenoid Hydrocarbons. Electrophilic Substitution Reactions of Naphthalene and Substituted Naphthalenes.

VI. CARBONYL COMPOUNDS.

16. Carbonyl Compounds I: Reactions of Carboxylic Acids and Their Derivatives with Oxygen and Nitrogen Nucleophiles.

Acidity of ...a-Hydrogens. Keto-Enol Tautomerism. Reactivity Considerations. Halogenation of the ...a-Carbon of Aldehydes and Ketones. Halogenation of the ...a-Carbon of Carboxylic Acids: The Hell-Volhard-Zelinski Reaction. ...a-Halogenated Carbonyl Compounds in Synthesis. Using Lithium Diisopropylamide (LDA) to Form an Enolate. Alkylation of the ...a-Carbon of Carbonyl Compounds. Alkylation and Acylation of the ...a-Carbon via an Enamine Intermediate. Alkylation of the ...b-Carbon: The Michael Reaction. The Aldol Addition. Dehydration of Aldol Addition Products: Formation of ...ab-Unsaturated Aldehydes and Ketones. The Mixed Aldol Addition. The Claisen Condensation. The Mixed Claisen Condensation. Intramolecular Condensation and Addition Reactions. Decarboxylation of 3-Oxocarboxylic Acids. The Malonic Ester Synthesis: Synthesis of Carboxylic Acids. The Acetoacetic Ester Synthesis: Synthesis of Methyl Ketones. Designing a Synthesis VI: Making New Carbon-Carbon Bonds. Reactions at the ...a-Carbon in Biological Systems.

Functional Group Introduction, Removal. and Interconversion. More about Retrosynthetic Analysis: Disconnections. Retrosynthetic Analysis of Dioxygenated Compounds. More about Protecting Groups. Control of Stereochemistry. Selected Examples of Syntheses.

Physical Properties of Organic Compounds. PKa Values. Derivations of Rate Laws. Summary of Methods Used to Synthesize a Particular Functional Group. Summary of Methods Used to Form Carbon-Carbon Bonds. Spectroscopy Tables.

Other Editions of Organic Chemistry

For full-year courses in organic chemistry taken by science and pre-health professions majors.

This innovative text from acclaimed educator Paula Bruice is organized in a way that discourages rote memorization. It highlights mechanistic similarities and ties synthesis and reactivity together--teaching the reactivity of a functional group and the synthesis of compounds obtained as a result of that reactivity. Bruice's writing has been praised for anticipating students' questions and appeals to their need to learn visually and by solving problems. Emphasizing that students should reason their way to solutions rather than memorize facts, Bruice encourages students to think about what they have learned previously and apply that knowledge in a new setting. The text balances coverage of traditional topics with bioorganic chemistry, recognizing the importance of bioorganic topics to today's students.

Features

ISSUE: Students need pedagogy created by an experienced instructor who understands where they need help. PROBE: Will your students benefit from a text written by an instructor familiar with their struggles?

NEW--Revised many of the boxed materials--Bring topics to life and demonstrate the real-world relevance of the chemistry students are learning.

Piques student interest, increases confidence, and provides extra help for those who need it.

PROBLEM-SOLVING ISSUE: Students need to practice, practice, practice by solving problems. PROBE: Would your students benefit from a text particularly rich in problems and problem-solving pedagogy?

NEW--More in-chapter problems, more end-of-chapter problems, and more solved problems than almost any other textbook.

Helps students master the subject through problem solving.

NEW--Review of functional groups at beginning of Chapter 12. More spectroscopy problems added to chapters following treatment of spectroscopy (Chapters 12 and 13).

Allows instructors to introduce spectroscopy early in the course; improves instructors' ability to integrate spectroscopy throughout the second half of the course.

Problem-solving strategies--Offers at least one per chapter, followed by an exercise that enables students to immediately practice the strategy just discussed.

Teaches students how to approach certain kinds of problems, organize their thoughts, and improve their problem-solving abilities.

Solved problems--Walk students carefully through the different steps involved in solving a particular type of problem.

Gives students a framework to apply this process to other problems of the same type.

MEDIA ISSUE: Students' understanding can be greatly enhanced by a media package that is tightly correlated to the text. PROBE: Would integrated media resources, which expand the book's effectiveness improve your students' understanding of organic chemistry?

(NOTE: Each chapter concludes with Key Terms and Problems. Chapters 3, 7-11, 14-20, and 27 conclude with a Summary of Reactions.)

I. AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY.

1. Electronic Structures and Bonding. Acids and Bases.

The Structure of an Atom. Distribution of Electrons in an Atom. Ionic, Covalent, and Polar Bonds. Lewis Structures. Atomic Orbitals. Molecular Orbitals and Bonding. Bonding in Methane and Ethane. Single Bonds. Bonding in Ethane. Double Bonds. Bonding in the Ethyne. Bonding in the Methyl Cation, the Methyl Radical, and the Methyl Anion. Bonding in Water. Bonding in Ammonia and in the Ammonium Ion. Bonding in the Hydrogen Halides. Summary of Orbital Hybridization, Bond Lengths, Bond Strengths, and Bond Angles. Dipole Moments of Molecules. An Introduction to Acids and Bases. Organic Acids and Bases: pKa and pH. The Effect of Structure on pKa. An Introduction to Delocalized Electrons and Resonance. The Effect of pH on the Structure of an Organic Compound. Lewis Acids and Bases.

2. An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure.

General Molecular Formula for a Hydrocarbon. Nomenclature of Alkenes. The Structure of Alkenes. Cis-Trans Isomerism. The E,Z System of Nomenclature. Reactivity Considerations. Thermodynamics and Kinetics. General Mechanism for Electrophilic Addition Reactions. Addition of Hydrogen Halides. Carbocation Stability. The Structure of the Transition State. Regioselectivity of Electrophilic Addition Reactions: Markovnikov's Rule. Addition of Water and Alcohols. Rearrangement of Carbocations. Addition of Halogens. Oxymercuration-Demercuration. Addition of Borane: Hydroboration-Oxidation. Addition of Radicals. The Relative Stabilities of Radicals. Addition of Hydrogen. The Relative Stabilities of Alkenes. Reactions and Synthesis.

4. Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions.

Conformational Isomers. Configurational Isomers: Cis-Trans Isomers. Configurational Isomers: Isomers with One Chirality Center. Drawing Enantiomers. Naming Enantiomers: The R, S System of Nomenclature. Optical Rotation. Optical Purity. Isomers with More Than One Chirality Center. Meso Compounds. The R, S System of Nomenclature for Isomers with More Than One Chirality Center. Reactions of Compounds That Contain a Chirality Center. Determining the Configuration. Separation of Enantiomers. Enantiotopic Hydrogens. Diastereotopic Hydrogens. and Prochirality Centers. Nitrogen and Phosphorus Chirality Centers. Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions. Stereochemistry of Alkene Addition Reactions. Stereochemistry of Enzyme-Catalyzed Reactions.

5. Reactions of Alkynes. Introduction to Multistep Synthesis.

Nomenclature of Alkynes. Physical Properties of Unsaturated Hydrocarbons. The Structure of Alkynes. Reactivity Considerations. Addition of Hydrogen Halides and Addition of Halogens. Addition of Water. Addition of Borane: Hydroboration-Oxidation. Addition of Hydrogen. Acidity of a Hydrogen Bonded to an sp Hybridized Carbon. Synthesis Using Acetylide Ions. Designing a Synthesis I: An Introduction to Multistep Synthesis. Commercial Use of Ethyne.

6. Electron Delocalization and Resonance.

Delocalized Electrons: The Structure of Benzene. Bonding in Benzene. Delocalized Electrons and Resonance. How to Draw Resonance Contributors. The Resonance Hybrid. Resonance Energy. Stability of Allylic and Benzylic Cations. Stability of Allylic and Benzylic Radicals. Some Chemical Consequences of Electron Delocalization. Effect of Delocalized Electrons on pKa. A Molecular Orbital Description of Stability.

7. Reactions of Dienes.

Nomenclature of Alkenes with More Than One Functional Group. Configurational Isomers of Dienes. Relative Stabilities of Dienes. A Molecular Orbital Description of 1,3-Butadiene. Reactivity Considerations. Electrophilic Addition Reactions of Isolated Dienes. Electrophilic Addition Reactions of Conjugated Dienes. Thermodynamic versus Kinetic Control of Reactions. Addition of a Dienophile to a Conjugated Diene: The Diels-Alder Reaction. Nomenclature of Bicyclic Compounds.

Reactivity Considerations. The Mechanism of SN2 Reactions. The SN2 Reaction. The Reversibility of an SN2 Reaction. The Mechanism of SN1 Reactions. The SN1 Reaction. The Stereochemistry of SN2 and SN1 Reactions. Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides. Competition between SN2 and SN1 Reactions. The Role of the Solvent in SN2 and SN1 Reactions. Biological Methylating Agents.

Nomenclature of Subsitituted Benzenes. Reactions of Substituents on Benzene. The Effect of Substituents on Reactivity. The Effect of Substituents on Orientaiton. The Effect of Substituents on pKa. The Ortho/Para Ratio. Additional Consideration Regarding Substituent Effects. Designing a Synthesis III: Synthesis of Monosubstituted and Disubstitued Benzenes. Synthesis of Trisubstitued Benzenes. Synthesis of Substitued Benzenes Using Arenadiazonium Salts. The Arenadiazonium Ion as an Electrophile. Mechanism for the Reaction of Amines with Nitrous Acid. Nucleophilic Aromatic Substitution Reactions. Benzyne. Polycyclic Benzenoid Hydrocarbons. Electrophilic Substitution Reactions of Naphthalene and Substituted Naphthalenes.

VI. CARBONYL COMPOUNDS.

16. Carbonyl Compounds I: Reactions of Carboxylic Acids and Their Derivatives with Oxygen and Nitrogen Nucleophiles.

Acidity of ...a-Hydrogens. Keto-Enol Tautomerism. Reactivity Considerations. Halogenation of the ...a-Carbon of Aldehydes and Ketones. Halogenation of the ...a-Carbon of Carboxylic Acids: The Hell-Volhard-Zelinski Reaction. ...a-Halogenated Carbonyl Compounds in Synthesis. Using Lithium Diisopropylamide (LDA) to Form an Enolate. Alkylation of the ...a-Carbon of Carbonyl Compounds. Alkylation and Acylation of the ...a-Carbon via an Enamine Intermediate. Alkylation of the ...b-Carbon: The Michael Reaction. The Aldol Addition. Dehydration of Aldol Addition Products: Formation of ...ab-Unsaturated Aldehydes and Ketones. The Mixed Aldol Addition. The Claisen Condensation. The Mixed Claisen Condensation. Intramolecular Condensation and Addition Reactions. Decarboxylation of 3-Oxocarboxylic Acids. The Malonic Ester Synthesis: Synthesis of Carboxylic Acids. The Acetoacetic Ester Synthesis: Synthesis of Methyl Ketones. Designing a Synthesis VI: Making New Carbon-Carbon Bonds. Reactions at the ...a-Carbon in Biological Systems.

Functional Group Introduction, Removal. and Interconversion. More about Retrosynthetic Analysis: Disconnections. Retrosynthetic Analysis of Dioxygenated Compounds. More about Protecting Groups. Control of Stereochemistry. Selected Examples of Syntheses.

Physical Properties of Organic Compounds. PKa Values. Derivations of Rate Laws. Summary of Methods Used to Synthesize a Particular Functional Group. Summary of Methods Used to Form Carbon-Carbon Bonds. Spectroscopy Tables.

Summary

For full-year courses in organic chemistry taken by science and pre-health professions majors.

This innovative text from acclaimed educator Paula Bruice is organized in a way that discourages rote memorization. It highlights mechanistic similarities and ties synthesis and reactivity together--teaching the reactivity of a functional group and the synthesis of compounds obtained as a result of that reactivity. Bruice's writing has been praised for anticipating students' questions and appeals to their need to learn visually and by solving problems. Emphasizing that students should reason their way to solutions rather than memorize facts, Bruice encourages students to think about what they have learned previously and apply that knowledge in a new setting. The text balances coverage of traditional topics with bioorganic chemistry, recognizing the importance of bioorganic topics to today's students.

Features

ISSUE: Students need pedagogy created by an experienced instructor who understands where they need help. PROBE: Will your students benefit from a text written by an instructor familiar with their struggles?

NEW--Revised many of the boxed materials--Bring topics to life and demonstrate the real-world relevance of the chemistry students are learning.

Piques student interest, increases confidence, and provides extra help for those who need it.

PROBLEM-SOLVING ISSUE: Students need to practice, practice, practice by solving problems. PROBE: Would your students benefit from a text particularly rich in problems and problem-solving pedagogy?

NEW--More in-chapter problems, more end-of-chapter problems, and more solved problems than almost any other textbook.

Helps students master the subject through problem solving.

NEW--Review of functional groups at beginning of Chapter 12. More spectroscopy problems added to chapters following treatment of spectroscopy (Chapters 12 and 13).

Allows instructors to introduce spectroscopy early in the course; improves instructors' ability to integrate spectroscopy throughout the second half of the course.

Problem-solving strategies--Offers at least one per chapter, followed by an exercise that enables students to immediately practice the strategy just discussed.

Teaches students how to approach certain kinds of problems, organize their thoughts, and improve their problem-solving abilities.

Solved problems--Walk students carefully through the different steps involved in solving a particular type of problem.

Gives students a framework to apply this process to other problems of the same type.

MEDIA ISSUE: Students' understanding can be greatly enhanced by a media package that is tightly correlated to the text. PROBE: Would integrated media resources, which expand the book's effectiveness improve your students' understanding of organic chemistry?

Author Bio

Table of Contents

Table of Contents

(NOTE: Each chapter concludes with Key Terms and Problems. Chapters 3, 7-11, 14-20, and 27 conclude with a Summary of Reactions.)

I. AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY.

1. Electronic Structures and Bonding. Acids and Bases.

The Structure of an Atom. Distribution of Electrons in an Atom. Ionic, Covalent, and Polar Bonds. Lewis Structures. Atomic Orbitals. Molecular Orbitals and Bonding. Bonding in Methane and Ethane. Single Bonds. Bonding in Ethane. Double Bonds. Bonding in the Ethyne. Bonding in the Methyl Cation, the Methyl Radical, and the Methyl Anion. Bonding in Water. Bonding in Ammonia and in the Ammonium Ion. Bonding in the Hydrogen Halides. Summary of Orbital Hybridization, Bond Lengths, Bond Strengths, and Bond Angles. Dipole Moments of Molecules. An Introduction to Acids and Bases. Organic Acids and Bases: pKa and pH. The Effect of Structure on pKa. An Introduction to Delocalized Electrons and Resonance. The Effect of pH on the Structure of an Organic Compound. Lewis Acids and Bases.

2. An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure.

General Molecular Formula for a Hydrocarbon. Nomenclature of Alkenes. The Structure of Alkenes. Cis-Trans Isomerism. The E,Z System of Nomenclature. Reactivity Considerations. Thermodynamics and Kinetics. General Mechanism for Electrophilic Addition Reactions. Addition of Hydrogen Halides. Carbocation Stability. The Structure of the Transition State. Regioselectivity of Electrophilic Addition Reactions: Markovnikov's Rule. Addition of Water and Alcohols. Rearrangement of Carbocations. Addition of Halogens. Oxymercuration-Demercuration. Addition of Borane: Hydroboration-Oxidation. Addition of Radicals. The Relative Stabilities of Radicals. Addition of Hydrogen. The Relative Stabilities of Alkenes. Reactions and Synthesis.

4. Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions.

Conformational Isomers. Configurational Isomers: Cis-Trans Isomers. Configurational Isomers: Isomers with One Chirality Center. Drawing Enantiomers. Naming Enantiomers: The R, S System of Nomenclature. Optical Rotation. Optical Purity. Isomers with More Than One Chirality Center. Meso Compounds. The R, S System of Nomenclature for Isomers with More Than One Chirality Center. Reactions of Compounds That Contain a Chirality Center. Determining the Configuration. Separation of Enantiomers. Enantiotopic Hydrogens. Diastereotopic Hydrogens. and Prochirality Centers. Nitrogen and Phosphorus Chirality Centers. Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions. Stereochemistry of Alkene Addition Reactions. Stereochemistry of Enzyme-Catalyzed Reactions.

5. Reactions of Alkynes. Introduction to Multistep Synthesis.

Nomenclature of Alkynes. Physical Properties of Unsaturated Hydrocarbons. The Structure of Alkynes. Reactivity Considerations. Addition of Hydrogen Halides and Addition of Halogens. Addition of Water. Addition of Borane: Hydroboration-Oxidation. Addition of Hydrogen. Acidity of a Hydrogen Bonded to an sp Hybridized Carbon. Synthesis Using Acetylide Ions. Designing a Synthesis I: An Introduction to Multistep Synthesis. Commercial Use of Ethyne.

6. Electron Delocalization and Resonance.

Delocalized Electrons: The Structure of Benzene. Bonding in Benzene. Delocalized Electrons and Resonance. How to Draw Resonance Contributors. The Resonance Hybrid. Resonance Energy. Stability of Allylic and Benzylic Cations. Stability of Allylic and Benzylic Radicals. Some Chemical Consequences of Electron Delocalization. Effect of Delocalized Electrons on pKa. A Molecular Orbital Description of Stability.

7. Reactions of Dienes.

Nomenclature of Alkenes with More Than One Functional Group. Configurational Isomers of Dienes. Relative Stabilities of Dienes. A Molecular Orbital Description of 1,3-Butadiene. Reactivity Considerations. Electrophilic Addition Reactions of Isolated Dienes. Electrophilic Addition Reactions of Conjugated Dienes. Thermodynamic versus Kinetic Control of Reactions. Addition of a Dienophile to a Conjugated Diene: The Diels-Alder Reaction. Nomenclature of Bicyclic Compounds.

Reactivity Considerations. The Mechanism of SN2 Reactions. The SN2 Reaction. The Reversibility of an SN2 Reaction. The Mechanism of SN1 Reactions. The SN1 Reaction. The Stereochemistry of SN2 and SN1 Reactions. Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides. Competition between SN2 and SN1 Reactions. The Role of the Solvent in SN2 and SN1 Reactions. Biological Methylating Agents.

Nomenclature of Subsitituted Benzenes. Reactions of Substituents on Benzene. The Effect of Substituents on Reactivity. The Effect of Substituents on Orientaiton. The Effect of Substituents on pKa. The Ortho/Para Ratio. Additional Consideration Regarding Substituent Effects. Designing a Synthesis III: Synthesis of Monosubstituted and Disubstitued Benzenes. Synthesis of Trisubstitued Benzenes. Synthesis of Substitued Benzenes Using Arenadiazonium Salts. The Arenadiazonium Ion as an Electrophile. Mechanism for the Reaction of Amines with Nitrous Acid. Nucleophilic Aromatic Substitution Reactions. Benzyne. Polycyclic Benzenoid Hydrocarbons. Electrophilic Substitution Reactions of Naphthalene and Substituted Naphthalenes.

VI. CARBONYL COMPOUNDS.

16. Carbonyl Compounds I: Reactions of Carboxylic Acids and Their Derivatives with Oxygen and Nitrogen Nucleophiles.

Acidity of ...a-Hydrogens. Keto-Enol Tautomerism. Reactivity Considerations. Halogenation of the ...a-Carbon of Aldehydes and Ketones. Halogenation of the ...a-Carbon of Carboxylic Acids: The Hell-Volhard-Zelinski Reaction. ...a-Halogenated Carbonyl Compounds in Synthesis. Using Lithium Diisopropylamide (LDA) to Form an Enolate. Alkylation of the ...a-Carbon of Carbonyl Compounds. Alkylation and Acylation of the ...a-Carbon via an Enamine Intermediate. Alkylation of the ...b-Carbon: The Michael Reaction. The Aldol Addition. Dehydration of Aldol Addition Products: Formation of ...ab-Unsaturated Aldehydes and Ketones. The Mixed Aldol Addition. The Claisen Condensation. The Mixed Claisen Condensation. Intramolecular Condensation and Addition Reactions. Decarboxylation of 3-Oxocarboxylic Acids. The Malonic Ester Synthesis: Synthesis of Carboxylic Acids. The Acetoacetic Ester Synthesis: Synthesis of Methyl Ketones. Designing a Synthesis VI: Making New Carbon-Carbon Bonds. Reactions at the ...a-Carbon in Biological Systems.

Functional Group Introduction, Removal. and Interconversion. More about Retrosynthetic Analysis: Disconnections. Retrosynthetic Analysis of Dioxygenated Compounds. More about Protecting Groups. Control of Stereochemistry. Selected Examples of Syntheses.

Physical Properties of Organic Compounds. PKa Values. Derivations of Rate Laws. Summary of Methods Used to Synthesize a Particular Functional Group. Summary of Methods Used to Form Carbon-Carbon Bonds. Spectroscopy Tables.